CN114516694A - Waste acid treatment process for co-production of sodium metabisulfite - Google Patents
Waste acid treatment process for co-production of sodium metabisulfite Download PDFInfo
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- CN114516694A CN114516694A CN202011304301.5A CN202011304301A CN114516694A CN 114516694 A CN114516694 A CN 114516694A CN 202011304301 A CN202011304301 A CN 202011304301A CN 114516694 A CN114516694 A CN 114516694A
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- Prior art keywords
- waste acid
- sodium metabisulfite
- tail gas
- sodium
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- 239000002699 waste material Substances 0.000 title claims abstract description 60
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 235000010262 sodium metabisulphite Nutrition 0.000 title claims abstract description 46
- 229940001584 sodium metabisulfite Drugs 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000010306 acid treatment Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 55
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 37
- 239000012452 mother liquor Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 239000010919 dye waste Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
- C01D5/145—Pyrosulfites or metabisulfites
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of nitroaniline wastewater treatment, and discloses a waste acid treatment process for co-producing sodium metabisulfite, which comprises the following steps: (1) stripping waste acid, (2) absorption reaction, (3) centrifugal separation, (4) drying and packaging and (5) tail gas treatment, wherein alkali liquor for absorbing the tail gas in the step (5) is saturated and then is mixed into sodium sulfite solution for absorbing sulfur dioxide in the step (2); the waste acid generated in the dye production process is used as a raw material for producing sodium metabisulfite, and after passing through a sodium metabisulfite production section, the waste acid is neutralized and can be directly sent to a subsequent wastewater treatment section.
Description
Technical Field
The invention relates to the technical field of nitroaniline wastewater treatment, in particular to a waste acid treatment process for co-producing sodium pyrosulfite.
Background
Acid is an important raw material in the dye industry, and a large amount of waste acid is generated in the production process of various dyes and intermediates. The prior waste acid treatment process generally needs pretreatment before entering a waste water device to neutralize acid to neutrality, and a large amount of alkali is consumed in the process, so that the treatment cost of the waste acid is increased.
The process for producing sodium metabisulfite generally adopts a specific method of sulfur or sulfur ore: firstly, crushing sulfur into powder, sending the powder to a combustion furnace by using compressed air, performing spontaneous combustion at the temperature of 600 plus 800 ℃ to obtain gas containing 10-13% of SO2, introducing the gas into a multistage reaction kettle to react with liquid alkali, crystallizing and separating foot sodium sulfate when the content of sodium bisulfite in the solution reaches a saturated concentration, and centrifuging, drying and packaging to obtain a sodium metabisulfite product. The traditional production process of sodium metabisulfite needs sulfur or sulfur ore as raw materials, and the production process taking waste acid as raw materials is not reported.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a waste acid treatment process for co-producing sodium metabisulfite, the waste acid generated in the dye production process is used as a raw material for producing the sodium metabisulfite, and after passing through a sodium metabisulfite production section, the waste acid is neutralized and can be directly sent to a subsequent wastewater treatment section.
In order to achieve the above purpose, the invention provides the following technical scheme:
a waste acid treatment process for co-producing sodium metabisulfite comprises the following steps:
(1) stripping waste acid: conveying the dye waste acid, mother liquor in an absorption section and sodium sulfite solid into a waste acid stripping device, wherein the waste acid stripping device is a stripping tower, the mixture of the waste acid, the mother liquor in the absorption section and sodium sulfite enters the stripping tower from the top of the tower, the waste acid reacts with the sodium sulfite to generate sulfur dioxide, hot air is introduced into the bottom of the stripping tower, liquid is in reverse contact with the air, the sulfur dioxide desorbed from the liquid enters an absorption reaction device along with the air, the waste acid in a liquid phase is neutralized through reaction with the sodium sulfite, the neutralized waste acid flows out from the bottom of the stripping tower to obtain gas containing the sulfur dioxide and the neutralized waste acid, and the neutralized waste acid enters other wastewater treatment devices for treatment;
(2) absorption reaction: introducing the gas containing sulfur dioxide obtained in the step (1) into a sodium sulfite solution for absorption, conveying tail gas to a tail gas treatment working section, crystallizing the sodium sulfite solution to separate out sodium metabisulfite, and conveying mother liquor containing sodium metabisulfite leaching to a centrifugal separation working section;
(3) centrifugal separation: centrifuging the mother liquor containing sodium metabisulfite leaching obtained in the step (2), separating to obtain sodium metabisulfite, conveying the sodium metabisulfite to a drying and packaging workshop, and conveying the mother liquor to a waste acid stripping section to continuously neutralize waste acid or mixing the waste acid with a sodium sulfite solution for absorbing sulfur dioxide;
(4) and (3) drying and packaging: drying and packaging the sodium metabisulfite wet product obtained by separation in the step (3) to obtain a product, and sending the generated waste gas into a tail gas treatment working section;
(5) tail gas treatment: and introducing the waste gas from the absorption reaction section and the drying and packaging section into a spraying alkali liquor to a tail gas absorption device for tail gas absorption treatment.
Preferably, the alkali liquor absorbing the tail gas in the step (5) is saturated and then mixed into the sodium sulfite solution absorbing the sulfur dioxide in the step (2), thereby realizing the reutilization of the alkali liquor.
Preferably, the alkali solution for absorbing the tail gas in the step (5) is a sodium hydroxide solution with a molar concentration of 10% -30%.
Preferably, the dye waste acid has acidity of 7%; the mass ratio of the dye waste acid added in the step (1), the mother liquor in the absorption section and the sodium sulfite solid is 30:10: 1.
Preferably, the sodium sulfite solution in the step (2) is prepared from sodium sulfite solid and desalted water, and the molar concentration of the sodium sulfite solution is 20-40%.
Compared with the prior art, the invention has the beneficial effects that:
the waste acid generated in the dye production process is used as a raw material for producing sodium metabisulfite, and after the sodium metabisulfite production section, the waste acid can be directly fed into a subsequent wastewater treatment section after being neutralized.
The waste acid raw material is used, and the generated sulfur dioxide gas does not contain dust like the sulfur dioxide gas generated by burning sulfur and sulfur ore, so that the gas washing process required in the traditional production flow is avoided, the sodium metabisulfite process flow is shortened, and the operation workload is reduced.
Drawings
FIG. 1 is a flow chart of the waste acid treatment process for co-producing sodium metabisulfite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a waste acid treatment process for co-producing sodium metabisulfite comprises the following steps:
(1) stripping waste acid: conveying the dye waste acid with acidity of 7%, mother liquor at an absorption section and sodium sulfite solid into a stripping tower according to the mass ratio of 30:10:1, allowing a mixture of the waste acid, the mother liquor at the absorption section and the sodium sulfite to enter the stripping tower from the tower top, allowing the waste acid to react with the sodium sulfite to generate sulfur dioxide, introducing hot air into the bottom of the stripping tower, allowing liquid to reversely contact with the hot air, allowing sulfur dioxide desorbed from the liquid to enter an absorption reaction device along with air, neutralizing the waste acid in a liquid phase by reacting with the sodium sulfite, allowing the neutralized waste acid to flow out from the bottom of the stripping tower to obtain gas containing sulfur dioxide and the neutralized waste acid, and allowing the neutralized waste acid to enter other wastewater treatment devices for treatment;
(2) absorption reaction: introducing the gas containing sulfur dioxide obtained in the step (1) into a sodium sulfite solution prepared from sodium sulfite solid and demineralized water for absorption, wherein the molar concentration of the sodium sulfite solution is 20-40%; the tail gas is sent to a tail gas treatment working section, sodium metabisulfite is separated out by crystallizing a sodium sulfite solution, and a mother liquor containing sodium metabisulfite leaching is sent to a centrifugal separation working section;
(3) centrifugal separation: centrifuging the mother liquor containing sodium metabisulfite leaching obtained in the step (2), separating to obtain sodium metabisulfite, conveying the sodium metabisulfite to a drying and packaging workshop, and conveying the mother liquor to a waste acid stripping section to continuously neutralize waste acid or mixing the waste acid with a sodium sulfite solution for absorbing sulfur dioxide;
(4) and (3) drying and packaging: drying and packaging the wet sodium metabisulfite product obtained by separation in the step (3) to obtain a product, and sending generated waste gas to a tail gas treatment section;
(5) tail gas treatment: introducing a sodium hydroxide solution with the spraying molar concentration of 10-30% into a tail gas absorption device for tail gas absorption treatment from waste gases from an absorption reaction section and a drying and packaging section; and (3) after the alkali liquor is saturated, mixing the saturated alkali liquor into the sodium sulfite solution used for absorbing sulfur dioxide in the step (2), thereby realizing the reutilization of the alkali liquor.
1400kg of dye waste acid with acidity of 7% consumes 450kg of sodium sulfite solid to carry out the process operation, and finally 346kg of sodium metabisulfite product with purity of 95% is obtained, and the acidity of the neutralized waste acid is reduced to 1%, so that the waste acid is neutralized, the treatment cost of the waste acid is reduced, and the resource saving effect is achieved;
by using the process, the use amount of 190kg of 30 percent liquid caustic soda can be reduced for each 1000kg of sodium sulfite, 247kg of sodium metabisulfite is produced, the operation cost is removed, and 216 yuan of economic benefit is generated, and the process can save 1.8 million yuan of waste acid treatment cost by supposing that the process replaces 20 million tons of sodium metabisulfite markets.
Meanwhile, the waste acid raw material is used, and the generated sulfur dioxide gas does not contain dust like sulfur dioxide gas generated by burning sulfur and sulfur ore, so that the gas washing process required in the traditional production flow is avoided, the sodium metabisulfite process flow is shortened, and the operation workload is reduced.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (6)
1. A waste acid treatment process for co-producing sodium metabisulfite is characterized by comprising the following steps:
(1) stripping waste acid: conveying the dye waste acid, mother liquor in an absorption section and sodium sulfite solid into a waste acid stripping device, carrying out gas stripping by using air to obtain gas containing sulfur dioxide and neutralized waste acid, and treating the neutralized waste acid in other wastewater treatment devices;
(2) absorption reaction: introducing the gas containing sulfur dioxide obtained in the step (1) into a sodium sulfite solution for absorption, conveying tail gas to a tail gas treatment working section, crystallizing the sodium sulfite solution to separate out sodium metabisulfite, and conveying mother liquor containing sodium metabisulfite leaching to a centrifugal separation working section;
(3) centrifugal separation: centrifuging the mother liquor containing sodium metabisulfite leaching obtained in the step (2), separating to obtain sodium metabisulfite, conveying the sodium metabisulfite to a drying and packaging workshop, and conveying the mother liquor to a waste acid stripping section to continuously neutralize waste acid or mixing the waste acid with a sodium sulfite solution for absorbing sulfur dioxide;
(4) and (3) drying and packaging: drying and packaging the wet sodium metabisulfite product obtained by separation in the step (3) to obtain a product, and sending generated waste gas to a tail gas treatment section;
(5) tail gas treatment: and introducing the waste gas from the absorption reaction section and the drying and packaging section into a spraying alkali liquor to a tail gas absorption device for tail gas absorption treatment.
2. A waste acid treatment process for co-producing sodium metabisulfite as claimed in claim 1, wherein the lye used for absorbing the tail gas in step (5) is saturated and then mixed into the sodium sulfite solution used for absorbing sulfur dioxide in step (2).
3. A waste acid treatment process for co-producing sodium metabisulfite as claimed in claim 2, wherein the lye used for absorbing the tail gas in step (5) is sodium hydroxide solution with a molar concentration of 10-30%.
4. A waste acid treatment process for co-producing sodium metabisulfite as claimed in claim 1, wherein the dye waste acid is a dye waste acid with acidity of 7%.
5. A waste acid treatment process for co-producing sodium metabisulfite as claimed in claim 4, wherein the mass ratio of the dye waste acid added in step (1), the mother liquor in absorption section and the sodium sulfite solid is 30:10: 1.
6. A waste acid treatment process for co-producing sodium metabisulfite as claimed in claim 1, wherein in step (2), the sodium sulfite solution is prepared from sodium sulfite solids and demineralized water, and the molar concentration of the sodium sulfite solution is 20-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011304301.5A CN114516694A (en) | 2020-11-19 | 2020-11-19 | Waste acid treatment process for co-production of sodium metabisulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011304301.5A CN114516694A (en) | 2020-11-19 | 2020-11-19 | Waste acid treatment process for co-production of sodium metabisulfite |
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| Publication Number | Publication Date |
|---|---|
| CN114516694A true CN114516694A (en) | 2022-05-20 |
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| CN202011304301.5A Pending CN114516694A (en) | 2020-11-19 | 2020-11-19 | Waste acid treatment process for co-production of sodium metabisulfite |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293533A (en) * | 2015-11-20 | 2016-02-03 | 潜江永安药业股份有限公司 | Pure oxygen production method of sodium pyrosulfite |
| CN105293534A (en) * | 2015-12-03 | 2016-02-03 | 攀枝花钢企欣宇化工有限公司 | Method for producing sodium sulfite solution by using sulfur dioxide gas |
| CN107089671A (en) * | 2016-02-18 | 2017-08-25 | 金昌正旭工贸有限责任公司 | A kind of wet process technique of sodium pyrosulfite |
| CN109626696A (en) * | 2019-01-29 | 2019-04-16 | 连云港清泰化工有限公司 | A kind of recovery processing technique of vulcanized sodium and sodium sulfite composite waste |
-
2020
- 2020-11-19 CN CN202011304301.5A patent/CN114516694A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293533A (en) * | 2015-11-20 | 2016-02-03 | 潜江永安药业股份有限公司 | Pure oxygen production method of sodium pyrosulfite |
| CN105293534A (en) * | 2015-12-03 | 2016-02-03 | 攀枝花钢企欣宇化工有限公司 | Method for producing sodium sulfite solution by using sulfur dioxide gas |
| CN107089671A (en) * | 2016-02-18 | 2017-08-25 | 金昌正旭工贸有限责任公司 | A kind of wet process technique of sodium pyrosulfite |
| CN109626696A (en) * | 2019-01-29 | 2019-04-16 | 连云港清泰化工有限公司 | A kind of recovery processing technique of vulcanized sodium and sodium sulfite composite waste |
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